Molecule-substrate interactions

In the case of chemisoriDtion this is the most exothennic process and the strong molecule substrate interaction results in an anchoring of the headgroup at a certain surface site via a chemical bond. This bond can be covalent, covalent with a polar part or purely ionic. As a result of the exothennic interaction between the headgroup and the substrate, the molecules try to occupy each available surface site. Molecules that are already at the surface are pushed together during this process. Therefore, even for chemisorbed species, a certain surface mobility has to be anticipated before the molecules finally anchor. Otherwise the evolution of ordered stmctures could not be explained. 

While cytochrome P-450 catalyzes the interaction with substrates, a final step of microsomal enzymatic system, flavoprotein NADPH-cytochrome P-450 reductase catalyzes the electron transfer from NADPH to cytochrome P-450. As is seen from Reaction (1), this enzyme contains one molecule of each of FMN and FAD. It has been suggested [4] that these flavins play different roles in catalysis FAD reacts with NADPH while FMN mediates electron... 

To provide information about the likely interactions of substrates and reaction intermediates with the enzyme, several important crystal structures have been analysed. The wild-type enzyme isolated from Bacillus stearo-thermophilus is a dimeric molecule (rmm ca. 90000) with 419 amino-acid residues per subunit, and a crystal structure to 300 pm resolution has been... 

Figure 5.7 The role of stress caused by lattice mismatch between SAM and substrate illustrated in (a) and (b) by a cross-section of a SAM (x-z plane), indicated adsorption sides (x-y plane) and the molecule-substrate interaction potential V where the solid circles indicate the energy of an adsorption site for a particular SAM molecule, (a) For rigid molecules, stress is mainly released by defect formation in SAM, which results in a layer of rather low crystallinity and small domains, (b) Molecules...

MICELLAR CATALYSIS. Chemical reactions can be accelerated by concentrating reactants on a micelle surface or by creating a favorable interfacial electrostatic environment that increases reactivity. This phenomenon is generally referred to as micellar catalysis. As pointed out by Bunton, the term micellar catalysis is used loosely because enhancement of reactivity may actually result from a change in the equilibrium constant for a reversible reaction. Because catalysis is strictly viewed as an enhancement of rate without change in a reaction s thermodynamic parameters, one must exercise special care to distinguish between kinetic and equilibrium effects. This is particularly warranted when there is evidence of differential interactions of substrate and product with the micelle. Micelles composed of optically active detergent molecules can also display stereochemical action on substrates. ... 

Tunnelling electrons from a STM have also been used to excite photon emission from individual molecules, as has been demonstrated for Zn(II)-etioporphyrin I, adsorbed on an ultrathin alumina film (about 0.5 nm thick) grown on a NiAl(l 10) surface (Qiu et al, 2003). Such experiments have demonstrated the feasibility of fluorescence spectroscopy with submolecular precision, since hght emission is very sensitive to tip position inside the molecule. As mentioned before the oxide spacer serves to reduce the interaction between the molecule and the metal. The weakness of the molecule-substrate interaction is essential for the observation of STM-excited molecular fluorescence. 

The analysis of such patterns reveals that the microcrystals are preferentially oriented with their (021) planes, the contact planes, parallel to the substrate s surface. The interesting point is that, in order to satisfy such orientation, the hydrogen bonds of the dimers at the interface have to be broken and in addition some reorganization of the molecules is needed (see Fig. 5.6(g)). In conclusion, the molecule-substrate interactions are sufficiently strong (larger yuns and y nv values) to induce COO Aik bonds, where Aik represents sodium and potassium, but the growing crystals adapt their structure in order to crystallize in the known monoclinic bulk phase. 

Electron damage and electronic excitation effects. Electron bombardment heating is suitable for the evaporation of all metals under vacuum, but its use in metal vapor synthesis can create problems because of electrons interacting with substrate molecules to form product-destroying ions or radicals. Electron... 

Receptor and substrate are terms describing the species involved in complex formation. Throughout the chapter the receptor will refer tp the macrocyclic ligand, the substrate to other interacting species. Substrates may be metal or molecular catibns, neutral molecules, or atomic or molecular anions. The terms receptor and substrate imply that the complex formed has the well-defined structural and chemical properties of a supermolecule, as in biological receptor-substrate associations. They exclude species formed only in the solid state (clathrates). They are also easily converted and understood in many languages. 

Enzymes are structurally complex, highly specific catalysts each enzyme usually catalyzes only one type of reaction. The enzyme surface binds the interacting molecules, or substrates, so that they are favorably disposed to react with one another (fig. 1.15). The specificity of enzyme catalysis also has a selective effect, so that only one of several potential reactions takes place. For example, a simple amino acid can be used in the synthesis of any of the four major classes of macromolecules or can simply be secreted as waste product (fig. 1.16). The fate of the amino acid is determined as much by the presence of specific enzymes as by its reactive functional groups. 

---